Catalyst for synthetic-methanol production



Patented Apr. 26, 1927.

UNITED STATES 1,625,927 PATENT OFFICE.

JOHN C. WOODR'UIT AND GROVER BLOOMFIELD, OF TERRE HAUTE, INDIANA, AS-

SIGNORS TO COMMERCIAL SOLVENTS CORPORATION, OF TERRE HAUTE, INDIANA,

A CORPORATION OF MARYLAND.

I CATALYST FOR SYNTHETIC-METHANOL PRODUCTION,

in: Drawing. Original application flied Kay 26, 1926, Serial No. 111,884. Divided and this application:

flied October 14, 1926. Serial No. 141,665. 1

Our invention relates to the production of methanol by the high pressure catalytic.

Carbon monoxide-CO 2H,2OH,OH

Carbon dioxide-430, 3H,2=CH,OH H O It is observed that when carbon dioxide is the oxide employed,'one molecule of water is formed for every molecule of methanol produced. On the other hand when pure carbon monoxide is used, theoretically there is nothing produced by the reaction but methanol. Actually in practice pure carbon ll monoxide and pure carbon dioxide are both diilicult to obtain economically, so that the methanol synthesis is carried out by reacting a mixture of carbon monoxide and carbon dioxide with hydrogen.

In addition to the reactions producing methanol there are, in the methanol synthesis, undesirable side-reactions which cutdown the yield of the desired product. The principal side reaction which ma occur is 36 the formation of methane, which is illustrated below:

produce methanol is passed over a catalytic substance comprising metals or their oxides at a pressure above atmospheres and at a anol catalysts proposed in the past have been of two principal types :-1. e.

1. Mixtures of finely divided metals, or,

what is equivalent, mixtures of easily reducible metal oxides;

2 Mixtures of oxides of metals non-reduclble, or difficulty reducible under the conditions of the methanol synthesis.

In the past, also, one class of easily reducible metal oxides, that is the ;oxides of iron, nickel, and cobalt have been described as absolutely worthless for the production of methanol catalysts since these metals under normal conditions prevent the formation of methanol, the reaction producing only methane.

We have discovered a new type of methanol catalyst which produces a higher yield of methanol than those formerly em loyed in the art, and at the same time pro was a very pure methanol, uncontaminated by byroducts. An additional advantage accrumg from the use of our catalysts is that the formation of methane in the process-with the consequent destruction of valuable hydrogen-is practically eliminated.

We have now discovered a new type of valuable methanol catalyst which comprises three main elements-i. e.

(1) One or more non-reducible metal oxides such as zinc, magnesium, cadmium, chromium, vanadium, tungsten, etc.;

(2) One or more easily reducible metal oxides such as copper, silver, iron, nickel,

, cobalt, etc.

sitions these normally deleterious substances serve advantageously, apparently exerting only a normal hydrogenating catalytic action productive of methanol. Or we may employ easily reducible oxides such as those of copper or silver which are already known in the art as advantageous components of certain methanol catalysts. In these cases however, our improved catalysts containing halides produce far better results than those known in the art for otherwise identical catalyst mixtures.

The precise method by which the metallic halides produce the improvement is not known to us. At least three theories may be used to account for the phenomenonnamely v (1) The metallic halide acts as an ordinary promoter in increasing catalyst activity;

(2) The metallic halide interacts with other metallic oxides present in the catalyst to produce oxychloride compounds which, in turn, either serve as catalyst promoters, or may so modify the urely physical state of the mass as to pro uce a more" active catalyst;

(3) The metallic halide may be reduced by the high pressure contact with hydrogen and carbon oxides during the commencement of its use as a catalyst and the resultant finely divided metal may increase the catalyst activity, or alternatively, the metallic halide may first react with some other metal producing the halide thereof, which may be reduced in the same manner.

However, the precise explanation for the improved result attained by the addition of metallic halides to methanol catalysts is not known and forms no part of our invention.

To produce our improved catalysts it is not necessary that the amount of metallic halide added bear any exact weight relation to the remaining constituents of the catalyst, though the amount of halide added should preferably be less than one chemical equivalent of the amount of rincipal metallic oxide present in the cata yst.

As illustrative of our invention we will cite two specific catalysts containing cobalt. In order to indicatethe comparative eflicacy of these catalysts in methanol roduction we have selected a standard set 0 conditions of use as follows. The reported yields of con densate from the methanol reaction by use of the followin catalysts is based on the effect produced w 1611 a gas mixture comprising 8% carbon dioxide, 3% of carbon monoxide and 89% hydrogen is passed throu h 1 liter of catalyst granules at a space ve ocity of 7 5,000-100,000, at a pressure of 2000 pounds, and at a temperatureof 340-400 C.

In selecting a standard set of conditions it is our intention only to thus display the catalyst eflicacy and by no means to limit the scope of our invention. Modification of the conditions of the reaction will, of course,

modify the results, but the results will always be proportionate to the catalyst employed.

For example, an increased space velocity produces an increased hourly yield and an increase in operating pressure has the same efl'ect. Llkewlse the use of pure carbon monoxide as distinguished from carbon (11- oxide or a mixture of the two results in an Emample I 2250 grams of cobalt nitrate (Co(NO GH O) are dissolved in 250 liters of water and the solution is heated to 95 C. There is then added 7.5 kilograms of zinc oxide after which the solution is vi orously stirred and sufiicient ammonium hydi'oxide is added to precipitate the cobalt as cobalt hydrate. The precipitated mass is recovered by decantation and filtration, is washed, ried, and broken up into granules. The granules are then moistened with a solution containing 1480 grams zinc chloride and dried once more.

The hourly yield of condensate is about 1.51liters and contains about 58% of methano Ewample II.

If the zinc chloride in Example I is replaced by 1300 grams of magnesium bromide the hourly yield of condensate and percentage yield of methanol is not greatly modified.

This application is a division of our copending application Serial No. 111 884, filed May 26th, 1926. In the said ap ication we have claimed, generically, met anol catalysts comprising diflicultly reducible metal oxides, easily reducible metal oxides, and metallic halides and therefore such generic claims are not made herein.

Now having described our invention, we claim the following as new and novel.

1. A methanol catalyst initially comprising a plurality of diflicultly reducible metal oxides, cobalt oxide, and a metallic halide.

2. A methanol catalyst initially comprising a diflicultly reducible metal oxide, cobalt oxide. and a metallic halide.

3. A methanol catalyst initially comprising zinc oxide, chromium oxide, cobalt oxide, and a metallic halide.

4. A methanol catalyst initially comprising zinc oxide, cobalt oxide, and a metallic halide.

5. A methanol catalyst initially comprising zinc oxide, chromium oxide, cobalt oxide, and zinc chloride.

6. A methanol catalyst initially comprising zinc oxide, cobalt oxide and zinc chloride. r l 7. 'A process for the production of synthetic methanol which comprises passing a mixture of hydrogen and carbon oxidesat a pressure m execs of 50 atmospheres and 15 at a temperature of 350450 '0'. over a tures.

catal st com rising" a reduc ible metal 0xide,. cobalt oxide and a r metallic halide.

9. A process a pressure in excess of 50 atmospheres, and

at a temperature of 350-450 C. over a r catalyst mitiallycom rising z'inc oxide, chromium oxide chloride. r r V In testimony whereof we afiix our signa-' JOHN v c; .wooDBUFF. enovnn BLOOMYFIELD. 1

for the production of syn- J 'thetic methanol which comprises a 20 mixture of hydrogen and carbon oxides at coba tloxlde and 

